US6313318B1 - Process for the preparation of α-methylene lactones - Google Patents
Process for the preparation of α-methylene lactones Download PDFInfo
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- US6313318B1 US6313318B1 US09/528,632 US52863200A US6313318B1 US 6313318 B1 US6313318 B1 US 6313318B1 US 52863200 A US52863200 A US 52863200A US 6313318 B1 US6313318 B1 US 6313318B1
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- BXXMQBGZZPULLM-UHFFFAOYSA-N C.C=C1C(=O)OC(C)(C)C1(C)C.CC1(C)CC(=O)OC1(C)C.CCOC Chemical compound C.C=C1C(=O)OC(C)(C)C1(C)C.CC1(C)CC(=O)OC1(C)C.CCOC BXXMQBGZZPULLM-UHFFFAOYSA-N 0.000 description 5
- OSLVLGCQJJQJDE-UHFFFAOYSA-N C.C=C1C(=O)OC(C)(C)C1(C)C.CC.CC1(C)CC(=O)OC1(C)C.CO Chemical compound C.C=C1C(=O)OC(C)(C)C1(C)C.CC.CC1(C)CC(=O)OC1(C)C.CO OSLVLGCQJJQJDE-UHFFFAOYSA-N 0.000 description 2
- LFCXHFZDUSIHNO-UHFFFAOYSA-N C=C(C(N)(N)/[O](/O1)=[I]\N=C)C1=O Chemical compound C=C(C(N)(N)/[O](/O1)=[I]\N=C)C1=O LFCXHFZDUSIHNO-UHFFFAOYSA-N 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/58—One oxygen atom, e.g. butenolide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
- C07C47/04—Formaldehyde
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
Definitions
- This invention concerns a process for the addition of formaldehyde to the ⁇ carbon atom of lactones to produce ⁇ -methylenelactones, and specifically ⁇ -methylene- ⁇ -butyrolactone.
- ⁇ -Methylene- ⁇ -butyrolactone is useful as a monomer in the preparation of both homopolymers and copolymers.
- the instant invention represents an advance in the art as it is a single step process that produces the desired product in high yields and good selectivity.
- the invention provides a process for preparing ⁇ -methylenelactones of Formula II comprising heating lactones of Formula I and formaldehyde in the vapor phase at a temperature of above 200° C. in the presence of a basic catalyst:
- n 1-11;
- R 1 , R 2 , R 3 , and R 4 taken independently are hydrogen, hydrocarbyl or substituted hydrocarbyl, C 1 -C 18 unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted cycloalkyl containing at least one heteroatom, unsubstituted or substituted aromatic ring, and unsubstituted or substituted aromatic ring containing at least one heteroatom.
- the lactone of Formula I is ⁇ -butyrolactone and the ⁇ -methylenelactone of Formula II is ⁇ -methylene- ⁇ -butyrolactone.
- Catalysts suitable in the present invention may be selected from the group consisting of metal oxides, metal hydroxides, and metal carbonates and may be supported or unsupported and may make use of catalyst promoters.
- n 1-11;
- R 1 , R 2 , R 3 , and R 4 taken independently are hydrogen, hydrocarbyl or substituted hydrocarbyl, C 1 -C 18 unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted cycloalkyl containing at least one heteroatom, unsubstituted or substituted aromatic ring, and unsubstituted or substituted aromatic ring containing at least one heteroatom;
- n 1-11;
- R 1 , R 2 , R 3 and R 4 taken independently are hydrogen, hydrocarbyl or substituted hydrocarbyl, C 1 -C 18 unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted cycloalkyl containing at least one heteroatom, unsubstituted or substituted aromatic ring, and unsubstituted or substituted aromatic ring containing at least one heteroatom,
- step (b) collecting the reactor effluent of step (a);
- the process of the present invention concerns an efficient methenylation of lactones to yield ⁇ -methylenelactones of which ⁇ -methylene- ⁇ -butyrolactone is a preferred member.
- the reaction proceeds according to the general scheme:
- n 1-11;
- R 1 , R 2 , R 3 , and R 4 taken independently are hydrogen, hydrocarbyl or substituted hydrocarbyl, C 1 -C 18 unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted cycloalkyl containing at least one heteroatom, unsubstituted or substituted aromatic ring, and unsubstituted or substituted aromatic ring containing at least one heteroatom.
- the lactone of Formula I is ⁇ -butyrolactone and the ⁇ -methylenelactone of Formula II is ⁇ -methylene- ⁇ -butyrolactone.
- R 1 , R 2 , R 3 , and R 4 may join to form members of a ring structure selected from the group consisting of, unsubstituted or substituted cycloalkyl, unsubstituted or substituted cycloalkyl containing at least one heteroatom in the ring, unsubstituted or substituted aromatic ring, and unsubstituted or substituted aromatic ring containing at least one heteroatom in the ring.
- Most preferred compounds are where the lactone of Formula I is ⁇ -butyrolactone and the ⁇ -methylenelactone of Formula II is ⁇ -methylene- ⁇ -butyrolactone.
- alkyl includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl and hexyl isomers. Also included are all isomers up to and including octadecane.
- hydrocarbyl group is a univalent group containing only carbon and hydrogen. If not otherwise stated, it is preferred that hydrocarbyl groups herein contain 1 to about 30 carbon atoms.
- substituted hydrocarbyl herein is meant a hydrocarbyl group which contains one or more substituent groups which are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially interfere with the process. If not otherwise stated, it is preferred that substituted hydrocarbyl groups herein contain 1 to about 30 carbon atoms. Included in the meaning of “substituted” are heteroaromatic rings.
- ⁇ -methylenelactones reactant of the present invention One of skill in the art will know where and how to obtain the ⁇ -methylenelactones reactant of the present invention.
- ⁇ -butyrolactone is readily available from commercial sources such as Aldrich Chemical Company (Millwaukee, Wis.).
- the process of the present invention is carried out in the vapor state, at temperatures greater than 200° C., over highly basic catalysts. Although any temperature above 200° C. is useful, temperature in the range of about 250° C. to about 400° C. are preferred where ranges of about 300° C. to about 340° C. are most preferred. In one preferred embodiment the lactone and formaldehyde of the present invention are in the vapor phase.
- the basic catalysts are selected from the metal oxides, hydroxides, and carbonates.
- the oxides, hydroxides and carbonates employed herein may be used as powders, granules, or other particulate forms, or may be supported on an essentially inert support as is common in the art of catalysis.
- Representative catalysts include but are not limited to of magnesium oxide, barium oxide, barium hydroxide, lanthanum oxide potassium hydroxide, cadmium oxide, rubidium oxide, lithium hydroxide, strontium hydroxide, sodium hydroxide, calcium hydroxide, barium carbonate and mixtures thereof.
- Preferred catalysts are barium hydroxide and lanthanum oxide, where barium hydroxide is most preferred.
- reaction conditions may result in the decrease of catalytic efficiency.
- contacting the present catalysts with O 2 at elevated temperatures has the effect of reactivating the catalyst.
- Contact temperatures with O 2 may range from about 300° C. to about 500° C. where temperatures of about 400° C. to about 425° C. are preferred.
- the metal oxide, hydroxide and carbonate catalysts of the present invention may further comprise catalyst additives and promoters which will enhance the efficiency of the catalyst.
- catalyst additives and promoters which will enhance the efficiency of the catalyst.
- Use of theses materials are common and well known in the art (see for example, Kirk - Othmer Encyclopedia of Chemical Technology, Howe-Grant Ed., Vol. 5, pp 326-346, (1993), John Wiley & Sons, New York and Ullmann's Encyclopedia of Industrial Chemistry, Vol. A5, Gerhartz et al., Eds., pp. 337-346, (1986), VCH Publishers, New York, both hereby incorporated by reference.)
- Particularly useful in the present invention is gold used as a promoter with BA(OH) 2 .
- Basic catalysts of the present invention may be supported or unsupported.
- suitable supports include but are not limited to silica, titania, zirconia, alumina, carbon, various zeolites and mixtures thereof.
- Particularly suitable catalyst—support combinations include barium hydroxide and lanthanum oxide supported on SiO 2 .
- Preferred catalysts of the present invention have been effective in producing product at good selectivities. Selectivities of greater than 50% are typical where selectivities of greater than 95% are common.
- selectivities and yields of product may be enhanced by additional contact with the catalyst.
- yields and selectivities may be increase where the reactor effluent containing a mixture of reactant and product may be passed one or more times over the catalyst under the reaction conditions to enhance the conversion of reactant to product.
- Formaldehyde may be supplied in a variety of forms including as a solution or in the form of a formaldehyde polymer.
- Polymers of formaldehyde are more generally denominated polyacetals and include or are characterized by a linear polymer chain containing recurring —(CH 2 O)— units or ggroups.
- a convenient form of formaldehyde was formalin, (37% aqueous formaldehyde).
- the desired products including ⁇ -methylene- ⁇ -butyrolactone
- are recovered using techniques common to the art. For example, when allowed to cool the ⁇ -methylene- ⁇ -butyrolactone reaction mixture forms a viscous, clear mass. Alternatively, when heated under vacuum, the ⁇ -methylene- ⁇ -butyrolactone/ ⁇ -butyrolactone mixture can be distilled directly from the reaction mixture. Additionally, the reaction mixture can be dissolved in water, adjusted to pH 4 with 6N HCl, then distilled. Similarly, the separation of ⁇ -methylene- ⁇ -butyrolactone from ⁇ -butyrolactone can be accomplished using vacuum distillation with a spinning band column.
- Another method to recover the desired product is to polymerize ⁇ -methylene- ⁇ -butyrolactone in the ⁇ -butyrolactone solution using standard free-radical polymerization, isolate the polymer by precipitation from methanol, then thermally depolymerize back to ⁇ -methylene- ⁇ -butyrolactone by heating under vacuum. Finally, ⁇ -methylene- ⁇ -butyrolactone may also be separated from - ⁇ -butyrolactone by melt crystallization.
- Table 1 summarizes the results of Examples 1-29.
- Ca(OH) 2 /SiO 2 NaOH/SiO 2 , LiOH/SiO 2 , Sr(OH) 2 /SiO 2 , KOH/SiO 2 and Ba(OH) 2 /SiO 2 gave yields exceeding 5%.
- the best overall catalyst was 8 wt % Ba(OH) 2 /SiO 2 which gave an 11% yield of ⁇ -methylene- ⁇ -butyrolactone at 37% conversion of the ⁇ -butyrolactone (37% product selectivity) at 340° C. No significant amounts of other volatile compounds were noted.
- the base oxides or hydroxides of Mg, Ca, Sr and Ba are active catalysts.
- the base oxides or hydroxides of Na, K and Rb(in combination with Mg) (Group IA) are active catalysts.
- These Groups include the most basic metal oxides known. Most of these materials were tested as deposited on an oxide support.
- the support material need not have a special character except that it should be stable to the reaction conditions. Metal oxides of Groups IVB and higher, up to Group IVA, are preferable. Rare earth oxides are also acceptable. It is believed that a support is preferred in order to maintain high catalyst surface areas.
- Table 2 shows examples (30-34) wherein feed ratios are varied. The most significant improvement in the % selectivities to ⁇ -methylene- ⁇ -butyrolactone came from variations in the reactant feed ratio. When the feed ratio was increased from 1:1 to 1:8 (lactone:formaldehyde) the average % yield increased as the ratio of formaldehyde increased.
- Example 37 identifies LiOH/Silica as an especially useful catalysts/support combination.
- Table 4 shows the formation of ⁇ -methylene- ⁇ -butyrolactone and ⁇ -methylene- ⁇ -butyrolactone using preferred catalyst (LaO/SiO 2 ) under varied conditions.
- Example 46 (Table 5) shows the ability to regenerate the catalyst Ba(OH) 2 /SiO 2 with air.
- Example 47 (Table 6) illustrates that there is enhanced conversion of ⁇ -butyrolactone to ⁇ -methylene butyrolactone if the reactor effluent is recycled across the catalyst a second time, indicating that a recycled procedure improves product yield.
- the Tables 1-6 contains the examples and show catalyst, nature and amount, feed ratio of ⁇ -butyrolactone to formalin, temperature, flow rate, observed conversion and yield or selectivity.
- silica-alumina powder ( ⁇ 150 m 2 g ⁇ 1 ) was slurried into a solution of 2 g Ba(OH) 2 octahydrate in 20 mL distilled water. The slurry was stirred for 10 minutes and then evaporated to dryness. The recovered solid was dried in a gold boat under flowing (100 mL/min) nitrogen at 550° C. for 2 hours and then collected under nitrogen as a granular white solid.
- b % Conversion (Moles of ⁇ -butyrolactone converted/moles of ⁇ -butyrolactone fed)*100
- c % Yield (Moles of ⁇ -methylene butyrolactone formed/Moles of ⁇ -butyrolactone converted)*100 ⁇ Parenthetical numbers indicate duplicate (repeats) runs
- b Conversion (Moles of ⁇ -butyrolactone converted/moles of ⁇ -butyrolactone fed)* 100
- c % Yield (Moles of ⁇ -methylene butyrolactone formed/Moles of ⁇ -butyrolactone converted)* 100
- Example 47 illustrates that the conversion of ⁇ -butyrolactone (GBL) to ⁇ -methylene butyrolactone (MBL) is enhanced if the reactor effluent is recyceld a second time through the reactor containing the catalyst.
- the molar ratio of GBL/MBL drops from 1 to 0.55 after a second exposure to the catalyst under reaction conditions, indicating further conversion of GBL to MBL.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
- Furan Compounds (AREA)
Priority Applications (1)
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US09/528,632 US6313318B1 (en) | 1999-03-30 | 2000-03-20 | Process for the preparation of α-methylene lactones |
Applications Claiming Priority (3)
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US12688399P | 1999-03-30 | 1999-03-30 | |
US12688499P | 1999-03-30 | 1999-03-30 | |
US09/528,632 US6313318B1 (en) | 1999-03-30 | 2000-03-20 | Process for the preparation of α-methylene lactones |
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US6313318B1 true US6313318B1 (en) | 2001-11-06 |
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US09/528,632 Expired - Fee Related US6313318B1 (en) | 1999-03-30 | 2000-03-20 | Process for the preparation of α-methylene lactones |
US09/536,350 Expired - Fee Related US6232474B1 (en) | 1999-03-30 | 2000-03-27 | Process for the preparation of α-methylenelactones and α-substituted hydrocarbylidene lactones |
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US09/536,350 Expired - Fee Related US6232474B1 (en) | 1999-03-30 | 2000-03-27 | Process for the preparation of α-methylenelactones and α-substituted hydrocarbylidene lactones |
Country Status (10)
Country | Link |
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US (2) | US6313318B1 (ko) |
EP (1) | EP1165536B1 (ko) |
JP (1) | JP2002540200A (ko) |
KR (1) | KR20010111581A (ko) |
CN (1) | CN1204131C (ko) |
AU (1) | AU3889900A (ko) |
BR (1) | BR0010768A (ko) |
CA (1) | CA2361037A1 (ko) |
DE (1) | DE60005318T2 (ko) |
WO (1) | WO2000058297A2 (ko) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003057686A1 (en) * | 2002-01-07 | 2003-07-17 | E.I. Du Pont De Nemours And Company | Alpha-methylenelactone synthesis in supercritical fluids |
US20030148214A1 (en) * | 2000-07-12 | 2003-08-07 | Tadayuki Fujiwara | Resins for resists and chemically amplifiable resist compositions |
US6649776B2 (en) | 2002-01-07 | 2003-11-18 | E. I. Du Pont De Nemours And Company | Methylenelactone synthesis in supercritical fluids |
US20040018442A1 (en) * | 2000-07-11 | 2004-01-29 | Yoon Kwang-Sub | Resist composition comprising photosensitive polymer having lactone in its backbone |
KR100428408B1 (ko) * | 2001-12-14 | 2004-04-28 | 학교법인 성균관대학 | α-메틸렌-γ-부티로락톤의 제조방법 |
US20060025609A1 (en) * | 2004-07-27 | 2006-02-02 | Hutchenson Keith W | Supercritical fluid phase synthesis of methylene lactones using oxynitride catlayst |
US20060025606A1 (en) * | 2004-07-27 | 2006-02-02 | Hutchenson Keith W | Gas phase synthesis of methylene lactones using oxinitride catalyst |
US20060025605A1 (en) * | 2004-07-27 | 2006-02-02 | Hutchenson Keith W | Supercritical fluid phase synthesis of methylene lactones using novel grafted catalyst |
US20060025611A1 (en) * | 2004-07-27 | 2006-02-02 | Hutchenson Keith W | Gas phase synthesis of methylene lactones using novel grafted catalyst |
US20060025612A1 (en) * | 2004-07-27 | 2006-02-02 | Hutchenson Keith W | Gas phase synthesis of methylene lactones using novel catalyst |
US20060084818A1 (en) * | 2004-10-18 | 2006-04-20 | Manzer Leo E | Gas phase synthesis of methylene lactones using catalysts derived from hydrotalcite precursors |
US20080293901A1 (en) * | 2007-05-25 | 2008-11-27 | Basf Corporation | Polymers and compounds prepared with alpha-methylene lactones, methods therefor, and coatings |
US8846817B2 (en) | 2010-11-11 | 2014-09-30 | Segetis, Inc. | Ionic polymers, method of manufacture, and uses thereof |
Families Citing this family (12)
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US6384846B1 (en) * | 1998-12-11 | 2002-05-07 | Hitachi America Ltd. | Methods and apparatus for rendering multiple images using a limited rendering resource |
DE60228576D1 (de) * | 2001-06-13 | 2008-10-09 | Magnachem Int Lab Inc | Lactonformulierungen und verfahren zur anwendung |
US7323495B2 (en) * | 2002-11-05 | 2008-01-29 | Magnachem International Laboratories, Inc. | Synthetic lactone formulations and method of use |
WO2005102315A1 (en) | 2004-04-23 | 2005-11-03 | Magnachem International Laboratories, Inc. | Synthetic lactone formulations for pain control |
US7199254B2 (en) * | 2004-07-27 | 2007-04-03 | E. I. Du Pont De Nemours And Company | Liquid phase synthesis of methylene lactones using novel catalyst |
US7141682B2 (en) * | 2004-07-27 | 2006-11-28 | E. I. Du Pont De Nemours And Company | Liquid phase synthesis of methylene lactones using oxnitride catalyst |
US7205416B2 (en) * | 2004-07-27 | 2007-04-17 | E. I. Du Pont De Nemours And Company | Liquid phase synthesis of methylene lactones using novel grafted catalyst |
US20060100449A1 (en) * | 2004-11-10 | 2006-05-11 | Manzer Leo E | Integrated two-step process for the production of gamma-methyl-alpha-methylene-gamma-butyrolactone from levulinic acid and hydrogen |
JP4642116B2 (ja) | 2006-08-22 | 2011-03-02 | 株式会社日本触媒 | 環状不飽和化合物の製造方法 |
KR20110128785A (ko) * | 2008-10-24 | 2011-11-30 | 매그나켐 인터내셔널 레버러토리즈 아이엔씨 | Rad9와 선택적으로 상호작용하는 화합물들의 스크리닝방법 |
KR101427092B1 (ko) * | 2012-01-13 | 2014-08-07 | 제일모직주식회사 | α-메틸렌락톤의 제조 방법 |
KR102379889B1 (ko) | 2021-05-17 | 2022-03-29 | 자경케미칼 주식회사 | 메틸렌 락톤계 화합물의 제조방법 |
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- 2000-03-16 KR KR1020017012528A patent/KR20010111581A/ko not_active Application Discontinuation
- 2000-03-16 AU AU38899/00A patent/AU3889900A/en not_active Abandoned
- 2000-03-16 JP JP2000608000A patent/JP2002540200A/ja active Pending
- 2000-03-16 WO PCT/US2000/006958 patent/WO2000058297A2/en not_active Application Discontinuation
- 2000-03-16 BR BR0010768-9A patent/BR0010768A/pt not_active IP Right Cessation
- 2000-03-16 CN CNB008040702A patent/CN1204131C/zh not_active Expired - Fee Related
- 2000-03-16 EP EP00918019A patent/EP1165536B1/en not_active Expired - Lifetime
- 2000-03-16 CA CA002361037A patent/CA2361037A1/en not_active Abandoned
- 2000-03-16 DE DE60005318T patent/DE60005318T2/de not_active Expired - Fee Related
- 2000-03-20 US US09/528,632 patent/US6313318B1/en not_active Expired - Fee Related
- 2000-03-27 US US09/536,350 patent/US6232474B1/en not_active Expired - Fee Related
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Cited By (29)
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US20040018442A1 (en) * | 2000-07-11 | 2004-01-29 | Yoon Kwang-Sub | Resist composition comprising photosensitive polymer having lactone in its backbone |
US20050008975A1 (en) * | 2000-07-11 | 2005-01-13 | Yoon Kwang-Sub | Resist composition comprising photosensitive polymer having lactone in its backbone |
US7241552B2 (en) | 2000-07-11 | 2007-07-10 | Samsung Electronics Co., Ltd. | Resist composition comprising photosensitive polymer having lactone in its backbone |
US7045267B2 (en) * | 2000-07-11 | 2006-05-16 | Samsung Electronics Co., Ltd. | Resist composition comprising photosensitive polymer having lactone in its backbone |
US20030148214A1 (en) * | 2000-07-12 | 2003-08-07 | Tadayuki Fujiwara | Resins for resists and chemically amplifiable resist compositions |
US6927011B2 (en) * | 2000-07-12 | 2005-08-09 | Mitsubishi Rayon Co., Ltd. | Resins for resists and chemically amplifiable resist compositions |
KR100428408B1 (ko) * | 2001-12-14 | 2004-04-28 | 학교법인 성균관대학 | α-메틸렌-γ-부티로락톤의 제조방법 |
WO2003057686A1 (en) * | 2002-01-07 | 2003-07-17 | E.I. Du Pont De Nemours And Company | Alpha-methylenelactone synthesis in supercritical fluids |
US6649776B2 (en) | 2002-01-07 | 2003-11-18 | E. I. Du Pont De Nemours And Company | Methylenelactone synthesis in supercritical fluids |
US7314942B2 (en) | 2002-01-07 | 2008-01-01 | E. I. Dupont De Nemours & Co. | Methylenelactones syntheses in supercritical fluids |
WO2006015022A1 (en) * | 2004-07-27 | 2006-02-09 | E.I. Dupont De Nemours And Company | Gas phase synthesis of methylene lactones using oxynitride catalyst |
US7151185B2 (en) | 2004-07-27 | 2006-12-19 | E. I. Du Pont De Nemours And Company | Gas phase synthesis of methylene lactones using oxynitride catalyst |
WO2006015019A1 (en) * | 2004-07-27 | 2006-02-09 | E.I. Dupont De Nemours And Company | Gas phase synthesis of methylene lactones using novel catalyst |
WO2006015021A1 (en) * | 2004-07-27 | 2006-02-09 | E.I. Dupont De Nemours And Company | Gas phase synthesis of methylene lactones using novel grafted catalyst |
US20060025611A1 (en) * | 2004-07-27 | 2006-02-02 | Hutchenson Keith W | Gas phase synthesis of methylene lactones using novel grafted catalyst |
WO2006028602A1 (en) * | 2004-07-27 | 2006-03-16 | E.I. Dupont De Nemours And Company | Supercritical fluid phase synthesis of methylene lactones using oxynitride catalyst |
US20060025609A1 (en) * | 2004-07-27 | 2006-02-02 | Hutchenson Keith W | Supercritical fluid phase synthesis of methylene lactones using oxynitride catlayst |
US20060025606A1 (en) * | 2004-07-27 | 2006-02-02 | Hutchenson Keith W | Gas phase synthesis of methylene lactones using oxinitride catalyst |
US20060025605A1 (en) * | 2004-07-27 | 2006-02-02 | Hutchenson Keith W | Supercritical fluid phase synthesis of methylene lactones using novel grafted catalyst |
US20060025612A1 (en) * | 2004-07-27 | 2006-02-02 | Hutchenson Keith W | Gas phase synthesis of methylene lactones using novel catalyst |
US7153981B2 (en) | 2004-07-27 | 2006-12-26 | E. I. Du Pont De Nemours And Company | Supercritical fluid phase synthesis of methylene lactones using oxynitride catalyst |
US7161014B2 (en) | 2004-07-27 | 2007-01-09 | E. I. Du Pont De Nemours And Company | Gas phase synthesis of methylene lactones using novel grafted catalyst |
US7164033B2 (en) | 2004-07-27 | 2007-01-16 | E. I. Du Pont De Nemours And Company | Gas phase synthesis of methylene lactones using novel catalyst |
US7166727B2 (en) | 2004-07-27 | 2007-01-23 | E. I. Du Pont De Nemours And Company | Supercritical fluid phase synthesis of methylene lactones using novel grafted catalyst |
WO2006044874A1 (en) * | 2004-10-18 | 2006-04-27 | E.I. Dupont De Nemours And Company | Gas phase synthesis of methylene lactones using catalysts derived from hydrotalcite precursors |
US20060084818A1 (en) * | 2004-10-18 | 2006-04-20 | Manzer Leo E | Gas phase synthesis of methylene lactones using catalysts derived from hydrotalcite precursors |
US7348442B2 (en) | 2004-10-18 | 2008-03-25 | E. I. Du Pont De Nemours And Company | Gas phase synthesis of methylene lactones using catalysts derived from hydrotalcite precursors |
US20080293901A1 (en) * | 2007-05-25 | 2008-11-27 | Basf Corporation | Polymers and compounds prepared with alpha-methylene lactones, methods therefor, and coatings |
US8846817B2 (en) | 2010-11-11 | 2014-09-30 | Segetis, Inc. | Ionic polymers, method of manufacture, and uses thereof |
Also Published As
Publication number | Publication date |
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DE60005318T2 (de) | 2004-07-08 |
DE60005318D1 (de) | 2003-10-23 |
JP2002540200A (ja) | 2002-11-26 |
CA2361037A1 (en) | 2000-10-05 |
AU3889900A (en) | 2000-10-16 |
WO2000058297A2 (en) | 2000-10-05 |
WO2000058297A3 (en) | 2001-02-08 |
EP1165536B1 (en) | 2003-09-17 |
EP1165536A2 (en) | 2002-01-02 |
CN1341112A (zh) | 2002-03-20 |
KR20010111581A (ko) | 2001-12-19 |
CN1204131C (zh) | 2005-06-01 |
US6232474B1 (en) | 2001-05-15 |
BR0010768A (pt) | 2002-01-15 |
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